Production of electrolytically-deposited gold in film or leaf form



ocms, 1929..

.w. F. GRUPE 1,731,415

PRODUCTION OF ELECTROLYTICALLY 'DEPOSITED GOLD IN FILI OR LEAF FORM FileFe 23, 1927'- 2 Sheets-Shea; l

Oct. 15, 1929. w. F. GRUPE I 1,731,415

PRODUCTI ON 0F ELECTROLYTICALLY DEPOSITED GOLD IN FILII OR LEAF FOR!Filed Feb. 23. 1927 2 Shuts-Sheet 2 ATToRNEY,

Patented Oct. 15, 1929 PATENT OFFICE WILLIAM F. GRUIfE, OF BUTHERFORIILFNEW JERSEY PRODUCTION OF ELE'GTROLYTICALLY-DEPOSITED GOLD IN FILM ORLEAF FORM Application filed February 23, 1927. Serial No. 170,152.

This invention relates to the production of electrolytically depositedgold in film or leaf form and mounted on an inert carrier such as paper.

Pursuant to my invention, a film or layer of gold is electrolyticallydeposited on a suitable cathode band of metal of high electricalconductivity, and such deposit of gold is mounted on the inert carrierby suitable procedure.

Preferably, silver is employed as the cathode band.

One method of mounting is by the use of grease-proof paper such asglassine paper,

cellophane or other inert carrier, on whicha continuous sheet ofindefinite length, protected by paper or other inert material of 1corresponding length,

My invention is adapted for immeaiaw use on the present market in theform of a heat releasable transfer medium embodying a continuous layerof electrolytic-ally deposited gold, adhered to the inhert carrier, suchas glassine paper, and suitable for use with a heated die in stamping orother impression machines.

Further features and objects of the invention Will be more fullyunderstood from the following detailed description and the accompanyingdrawings, in which 4 Fig. 1 is a diagram illustrating the, respectivesteps of electrolytic deposition pf gold on a metallic cathode band, andapplying to the deposited goldface of the cathode band a strip ofgreaseproof paper or other inert carrier material with the use of a waxyin- Fig. 2 is a diagram illustrating the treatment of the combinedcathode band, electrolytic gold deposit and inert carrier, for theremoval of the cathode band and deriving an endless length ofelectrolytically deposited gold applied by the intermediate heatreleasable medium to an endless carrier;

Fig. 3 is a sectional elevation on line 3-3 of Fig. 1, on a greatlyenlarged scale;

Fig. 4 is "a sectional elevation on line H of Fig. 2, on a greatlyenlarged scale; Fig. 5 is a sectional elevation similar to Fig. 4;, butshowing a modification of my invention in the removal of ,the cathodeband;

Fig. 6 is a cross-sectional view through a composite strip derived fromthe procedure, indicated in Fig. 5, and indicating the gauge of slittingto attain the desired final product;

Fig. 7 is a top plan view of a portion of a length of paper, to which awater and acid proof adhesive is applied at its opposite ends,illustrating an intermediate step of deriv- "ing an indefinite length ofgold freely mounted on an inert carrier;

Fig. 8 is a cross-sectional view of a composite strlp obtained by theuse of the step shown in Fig. 7, and indicating the gauge of slitting toderive a product pursuant to my invention; Fig. 9 illustrates a modifiedstep of employmg tissue paper in conjunctionwith the derived productindicated in Fig. 8; and Fig. 10 illustrates a roll of indefinite lengthof tissue paper and an intermediately Wound indefinite length of freelymounted gold film.

Referring to the diagram of Fig. 1, 1O represents an electrolytic bathof gold in any suitable form, such as a solution of the double cyanideof gold and potassium. The anode is indicated at 11, and is preferablyan insoluble anode such as platinum. The cathode may be in the form ofan endless band 12', preferably of silver, of a thickness of themagnitude of .001 of an inch, and preferably less, and of any desiredwidth, say four inches. Such cathode band 12 is passed continuouslysupplied in the form of a roll '13 and passed over a rotarily mounteddrum 14. The derived gold-silver band, designated 12 see Fig. 1, issuitably treated to remove any plating solution. lUsually I employ abath 15 of alkali to effectively free the band 12 of the platingsolution, andthereafter a bath 16 of water to remove any alkali carriedby the band 12 after submersion in the bath 15. The

band 12 is then preferably heated, say, by

the electrical heater 12 to dry the band.

Any desired number of rollers 17, or equiv alent, are employed forpassing the band 12 to and through the baths 15,16.

The electrical negative connection of a suitable source of electricalenergy with the silver band 12 during the electrolytic deposition stage,is employed, such as by means of the spring contact 18.

. The drum 14, about .which the cathode silver band 12 passes through.the plating bath, may be of hard rubber, wood or the like, which isinert and resistant to the gold plat-- ing solution '10. 1 j

I-prefer to use suitable means for preventing thedeposit of gold at the;opposite lateral edges of the silver band 12.- One suchdeosit-preventing means is indicated generally in Fig. 1 and in furtherdetail in Fig. 3, and comprises a belt 19 passed for the length of itsone lead 19 about the periphery of the drum 14 on one side of thecathode band 12 and its other lead l9 passed over a roller 19.

A similar band 20' protects the opposite latand are guided and retainedin position, by means of the oppositely disposed rollers 21, 22, one orboth of which may be positively driven, say, in the direction of thearrow 23,

see Fig. 1, and thereby rotate the drum 14 in the correspondingdirection indicated by the arrow 24. Positive means may be employed todrive the cathode drum 14 in the direction of the arrow 24, if desired.

Suitable means are provided for attaining a substantially uniformthickness of deposit, including the circulation of the plating solu tionfrom a suitable reservoir (not shown) to the tank 10, and imparting agentle motion to the anode 11, as by pivotally suspending the anode bymeans of'the arm 25, the upper end 26 of which arm 25 is oscillated bythe cam 27, carried by the drum 14, and operating'the link 28. The arm25 is shown pivoted to the bracket 29, secured to one side of the tank10.

Fig. 1 shows, in addition, the applying of the solution-free and driedgold-silver band to an indefinite length 30 of paper or like inertmaterial, such as glassine paper, cello phane, and the like, which maybe supplied in the form of a roll 31, thence passed about idlers 32 overthe feeding roll 33 for coating the under face of the glassine strip 30with a suitable binding material.

As indicated above, a preferred use of my new product is as a heatreleasable transfer medium for stamping and other impression machinesfor ornamentating objects with embossed, intaglio or otherornamentations with gold or, like material. For such purpose, a bath 34of the heat releasable material 34 is employed in fluid form, as byheating the same. For such purposelmay use a mixture of beeswax, rosinorother resin, or cumar, or any suitable phenol condensation products suchas phenol condensation products, furfurol products, or the. like. Theheat-releasable material in such fluid form may be fed from the bath 34by the roll 35 or equivalent to one side of the paper strip carrier 30.

The strip of paper now coated on its one face with the cooled layer ofthe binder is forced, see'36, between a pair of pressure rolls 37, 38against the gold deposited face of the silver band .12 to form aresulting composite silver-gold-binder-carrier band 39 of indefinitelength, which may be wound up as a roll 40. 1

Such composite stripof paper-binding medium-gold-silver is now suitablytreated to remove the silver band or layer. One procedure of removingthe silver is by uncoiling the roll 40, see Fig. 2, and passing itslength 41 through a bath 42 containingni: trio acid or the like fordissolving the silver layer, while retaining the gold film, bindingmedium and inert carrier immune to nitric acid or other silver-removingmedium, and preferably in a manner whereby the nitric acid or otherremoving medium is prevented from contacting with the layers of the com-,posite band other than the silver.

In Fig; 4 I have illustrated on an enlarged scale a form of a portion ofthe apparatus shown in. Fig. 2, whereby the composite band -41 isprogressed through the bath 42 sub-' stantially at the level 42 of thebath 42. It will be noted that the silver layer 41 is lowermost andbrought into direct contact with the nitric acid 42 or equivalent. Thegold film 41 is next adjacent to'the silver layer 41 To attain properprogression of the composite. band 41 through the bath 42, I provide aguide 43 in the form of a horizontally exrier 41 of a greater width thanthe silver layer 41, and thereby project at the opposite lateral edgesof the gold-silver layers, to cooperate with the oppositely disposedrods 48, 49, located above the level 42 of the bath 42 in the tank 45,and thus hold the opposite lateral edges of the paper 4l positivelyabove the bath 42, and hence prevent the upper surface of the paper 41from being wet. By such procedure, paper stock other than glassinepaper, may be successfully employed, by reason of the under surfacebeing coated with a water repellant layer suchasthe layer 41 of beeswax,rosin or other resins or equivalent, as set forth in detail hereinabove.

.After passage of the composite strip 41 through the nitric acid orequivalent bath 42, the band now indicated 50, and deprived of itsprevious silver layer 41, is passed into a bath 51 of alkali orequivalent, to remove any excess nitric acid, thence passed throughother baths 52, 53 of the number desired for removing alkali or othermoisture from the band 50, which at the stage designated is then dried.The band at the stage 50 is now formed of an outermost"(in this positionin Fig; 2 the lowermost) layer of gold film, next a layer of the'heat,releasable 'material or 7 other waxy and water repellant binding medium,and lastly, the paper carrier. A heater 50 may be employed to dry thecomposite -band5.

alent or shellac or other sizing, and apply-.

ing the desired. thickness of layer of sizing to the gold layer of theheat-releasable transfer strip in any suitable manner, as by means ofthe supplying roll 55 coacting with the applying roll 56, associatedwith the oppositely disposed guide rollers 57, 58, and then drying thesizing, as by means of an oven 59, preferably embodying a set of rollersdisposed to progress the strip 50 about a curved path to face the steamjacket 61 or equivalent'of the oven 59. The dried; sized heat-releasabletransfer strip may then be wound up as a roll 62.

If desired, the shellac or other sizing may be sprayed on the gold layerof the heatreleasable transfer strip.

In the de-silvering treatment, the composite silver-gold-binder-paperband may be passed, see Fi 5., through the nitric acid bath 42,substantia ly at the level 42 of the bath, to bend up a portion of theopposite lateral edges of the silver 41 and gold 41 as well as thebinder 41 and the paper 41", by means of the guide rods 48, whereby thederived band, see Fig. 6', has retained residual lateral strips 41 ofthe original silver band 41. Such residual strips 41 are removed by asuitable slitting machine, or equivalent, and

gold are substantially uniform throughout the length of the gold strip,whereas these properties of beaten gold leaf are non-uniform, whencompared leaf with leaf and the respective portions of any individualleaf.

In Fig. 7, I have illustrateda step-of a 1 modified form of myinvention, The strip 65 is of suitable material such as glassine paper,cellophane or the like, which may be .supplied in the form of a rollsimilar to the roll 31, in Fig. 1. In this modified form of myinvention, however, the adhesive, such as shellac, is applied by anapplying roll 33", co-

operating similar to the applying roll,33 of the adhesive applyingdevice shown in Fig.

1, to locate the shellac at narrow spaces 66, 66 at, the oppositelateral edges of the strip 65, whereby such shellac strip 65 is broughtinto contact with the gold deposited face of the silver band, similar tothe procedure in Fig. 1, the use of such modified form of adhesiveapplying roll 33 requiring the guide roll 32 to be displaced fromtheroll 33 a distance corresponding to the-height of lateral annular facesof the roll 33. Thereafter, the silver band or layer is removed by meansof nitric acid in a bath similar to the bath 42, see Fig. 2, andsubsequently treated as above described; in-this instance the compositestrip,

-see Fig. 8, is formed of the paper 65 secured b the spaced shellac 66,66, to the gold film 6% Such resultant composite strip may now beslitted for the desired gauge of slitting indicated by the doublearrowed line 68 to remove the shellacked outer edge portions of thepaper and the adhered outer edge portions of the gold. The resultingroll69, see Fig. 9, is formed of. convolutions of the carrier strip such asglassine paper, cellophane or the like, having the continuous film ofgold 67 wound freely between such convolutions; I

A roll of tissue paper or the like having a continuous stripof freelymounted electrolytic or other-film of gold may be derived by passing thecomposite glassine paper, shellac and gold, as illustrated in Fig. 8,jointly with a roll 70 of tissue paper in the manner indicated' in Fig.9, namely by feeding the tissue paper 70 to thegold face 67 of suchcomposite strip and into the slitting machine, thereby deriving acomposite roll 71 of desired width, each convolution of which is formedof a layer 70 of tissue paper, and an intermediate layer'of gold film 67and the opposite layer 65 of glassine paper or the like. By unrolling'such roll 71 to remove the glassine paper 65 there is obtained theresulting-roll 7 2, see Fig. 10, of the carrier strip 70 of tissue paperand the continuous film 67 of gold wound freely between thecon'volutions.

While it has been heretofore proposed and has been marketed genuine goldleaf in socalled roll form, such roll has been formed by employinggoldbeaters so-called gold 10 leaf, the individualleaves being appliedon a face of a length of paper, which may be rolled to a roll form,usually rouge or the like being employed to prevent the exposed faces ofthe leaves fromadhering to the reverse face of the roll paper. Bybeating goldv pursuant to the so-called goldbeaters meth- 0d, themaximum dimension attainable is approximately six or seven inches forleaves having a thickness of one one-thousandth of an inch or less, suchmaximum length being limited. by the ductility and other physicalcharacterlstics of gold. By reason ofmy process yielding gold film ofindefinite length as .may be desired for the purposes required, I

have employed the expression of a length materially greater than that ofbeaten gold todesignate in the claims a length of integral gold filmexceeding the maximum dimension of, goldbeaters gold leaf as may bedesired. ,Whereas I have described my invention by reference to specificforms thereof, it Will be understood that many changes and modificationsmay bemade without departing from the spirit of the invention.

I claim:

1. A heat releasable transfer strip comprising a strip of inert materialserving as a carrier, a layer of heat releasable medium on one face ofthe sameand a substantially continu- 0 ously integral layer of golddisposed on said layer of heat releasable material, said layer of goldhaving a length mate rially greater than that of beaten gold.

2. A heat releasable transfer strip com-- prising'a strip of inertmaterial serving as a carrier, a layer of heat releasable medium on oneface of the same and a layer of continuously integral gold deposited'onsaid layer of heat releasable material, said layer of gold beingsubstantially of uniform thickness throughout the length of the strip,said layer of gold having a length materially greater than that ofbeaten gold.

3. The method of forming a strip of gold supported by astrip of inertmaterial which comprises subjecting a continuous strip of metalas acathode to an electrolytic-bath containing gold .to thereby depositdirectly upon said cathode strip, a layer of gold, applying the derivedcomposite strip to a continuous I strip of the inert material serving asthe supporting strip to thegold face of the composite str p, anddissolving the metal strip while said layer of gold is supported'by saidcontinuous strip ofinert material, thereby continuously deriving a goldlayer supported by a continuous strip of inert material.

'4. The method of forming a strip of gold supported by a strip of inertmaterial which comprises subjecting a strip of metal as a cathode to anelectrolytic bath containing gold to thereby deposit directly upon suchstrip of metal a layer of gold, applying the derived composite strip toa strip of inert material serving as a supporting strip, such supportingstrip of inert material being applied to the layer of gold and the metalstrip being' outermost, and dissolving the metal strip from the goldlayer While the gold layer is supported by the strip of inert material.

5. The method of forming a strip of gold supported by a strip ofinertmaterial which comprises subjecting a continuous strip of metal asa cathode to an electrolytic bath containing gold to thereby depositdirectly upon such strip of metal a layer of gold, applying the derivedcomposite strip to' a continuous strip of inert material serving as asupporting strip, such supporting strip of iner material being appliedto the layer of gol and the metal strip being outermost, and dissolvingthe metal stripfrom the gold layer While the gold layer is supported bythe strip of inert material. 7

6. The method of forming a strip ofgold supported by a strip of inertmaterial which comprises subjecting a strip of metal as a cathode to anelectrolytic bath containinggold'to thereby. deposit directly upon such,strip of metal a layer of gold, applying the derived composite'strip toa strip of inert material serving'as a supporting strip by the use of aheat releasable medium, and dissolving the metal strip while the goldlayer is supported by the strip of inert material and at a temperaturelower than the heat releasing temperature of the heat releasable medium.

7. The method of forming a strip of gold supported by a strip of inertmaterial which comprises subjecting a strip of metal as a cathode to anelectrolytic bath containing gold ,to thereby deposit directly upon suchstrip of metal a layerof gold, applying the derived composite strip to astrip of inert material serving asa supporting strip by the use of aheat releasable medium, and dissolving the metal strip While the goldlayer is supported by the strip of inert material by the use of asolvent capable of dissolving the metal cathode strip and incapable ofdissolving the gold layer and the heat releasable inedium.

8. The method of forming a strip of gold supported by a strip of tissue1paper which comprises subjecting a strip 0 metal .as a cathode to anelectrolytic bath containing gold to thereby deposit directly upon saidstrip of metal a layerof gold, applying the derived composite strip to astrip of inert material serving as the supporting strip, dissolving themetal cathode strip while-the layer of gold is supportedby thesupporting strip of lnert material, and transferring the layer of goldfrom said supporting strip of inert material to a'strip of tlssue paper.

9. An impression transfer medium comprising a strip of inert material ofindefinite length serving as a carrier,'a substantially continuouslyintegral film of metal having a length materially greater than that ofbeaten gold,-said metallic film being secured to said carrier strip andreleasable b transfer. v i p 10. The method of forming a layer of Imetal supported upon a carrier strip which comprises subjecting acathode strip to an electrolytic bath containing the metal to therebydeposit upon the cathode strip the layer of the metal, applying thederived composite stri to a carrler strip and dissolving the catho estrip without substantial contact of the dissolving medium with thecarrier strip. n

In testimony whereof I have signed this specification this 21st day ofFebruary, 1927.

a WILLIAM F. GRUPE.

impression

